A novel organocatalytic cascade process initiated by 1,6-conjugated addition has been successfully developed. A range of pharmaceutically active 2-amino-4-aryl-4H-chromenes were readily obtained in high yields(88%-99...A novel organocatalytic cascade process initiated by 1,6-conjugated addition has been successfully developed. A range of pharmaceutically active 2-amino-4-aryl-4H-chromenes were readily obtained in high yields(88%-99%) and excellent enantiopurities(86%-99% ee). The functionalized para-Quinone methides(p-OMs) could be facilely obtained.展开更多
An intriguing Brønsted acid-catalyzed 1,6-hydrophosphination of in situ generated propargylic para-quinone methides(p-QMs)and aza-para-quinone methides(aza-p-QMs)with H-phosphorus oxides via dehydration/1,6-addit...An intriguing Brønsted acid-catalyzed 1,6-hydrophosphination of in situ generated propargylic para-quinone methides(p-QMs)and aza-para-quinone methides(aza-p-QMs)with H-phosphorus oxides via dehydration/1,6-addition under ultrasonic irradiation is described.This methodology provides a rapid and green approach for the construction of diarylmethyl phosphorus oxides bearing phosphorus-substituted quaternary carbon centers in high yields(up to 98%yield)within merely 5min.This environmentally benign protocol represents a unique example of 1,6-conjugate additions of propargylic p-QMs and aza-p-QMs for site-selective C-P bond formation in an operationally simple and atom-economical manner.The use of readily available Brønsted acid catalyst,operationally simplicity,high yields,and high atom economy make this protocol very facile,practical,easily scaled-up and environmentally friendly.展开更多
Five novel tropos (3R,4R)- and/or (3S,4S)-N-benzyltartarimide-derived biphenylphosphite ligands were synthesized and applied in the Cu-catalyzed asymmetric conjugate addition of diethylzinc to cyclic enones with u...Five novel tropos (3R,4R)- and/or (3S,4S)-N-benzyltartarimide-derived biphenylphosphite ligands were synthesized and applied in the Cu-catalyzed asymmetric conjugate addition of diethylzinc to cyclic enones with up to 75% e.e. Compared with the reported ligand 1-N-benzylpyrrolidine-3,4-bis[(R)-1,1'-binaphthyl-2,2'-diyl]phosphite- L-tartaric acid, the issue that L-(+)-tartaric acid backbone and (R)-binaphthyl showed strong matched/mismatched character was solved with these tropos ligands. It was found that the enantioselectivity was mainly controlled by the absolute configuration of N-benzyltartarimide backbone, and both enantiomers of the addition products can be obtained by simply changing the configuration of N-benzyltartarimide substituent.展开更多
基金国家重点研发项目(2022YFA1503200,2021YFC2101901)国家自然科学基金(22122103,21971108,21971111,22271144)+1 种基金中央高校基本科研业务费(020514380304,020514380252 and 020514380272)江苏省研究生科研与实践创新计划项目(KYCX22_0100).
基金financially supported by the National Natural Science Foundation of China(No.21402163)the Fundamental Research Funds for the Central Universities of Southwest Minzu University (No. 2016NGJPY02)+1 种基金the Graduate Innovation Project of Southwest Minzu University (No. CX2017SZ016)the Undergraduate Innovation Project of Southwest Minzu University (No. S201610656092)
文摘A novel organocatalytic cascade process initiated by 1,6-conjugated addition has been successfully developed. A range of pharmaceutically active 2-amino-4-aryl-4H-chromenes were readily obtained in high yields(88%-99%) and excellent enantiopurities(86%-99% ee). The functionalized para-Quinone methides(p-OMs) could be facilely obtained.
基金We are grateful for financial support from the National Natural Science Foundation of China(No.21762005)Natural Science Foundation of Guangxi Province(No.2021GXNSFDA075005).
文摘An intriguing Brønsted acid-catalyzed 1,6-hydrophosphination of in situ generated propargylic para-quinone methides(p-QMs)and aza-para-quinone methides(aza-p-QMs)with H-phosphorus oxides via dehydration/1,6-addition under ultrasonic irradiation is described.This methodology provides a rapid and green approach for the construction of diarylmethyl phosphorus oxides bearing phosphorus-substituted quaternary carbon centers in high yields(up to 98%yield)within merely 5min.This environmentally benign protocol represents a unique example of 1,6-conjugate additions of propargylic p-QMs and aza-p-QMs for site-selective C-P bond formation in an operationally simple and atom-economical manner.The use of readily available Brønsted acid catalyst,operationally simplicity,high yields,and high atom economy make this protocol very facile,practical,easily scaled-up and environmentally friendly.
基金Supported by the National Natural Science Foundation of China (Nos.20773147, 21073211, 21174133).
文摘Five novel tropos (3R,4R)- and/or (3S,4S)-N-benzyltartarimide-derived biphenylphosphite ligands were synthesized and applied in the Cu-catalyzed asymmetric conjugate addition of diethylzinc to cyclic enones with up to 75% e.e. Compared with the reported ligand 1-N-benzylpyrrolidine-3,4-bis[(R)-1,1'-binaphthyl-2,2'-diyl]phosphite- L-tartaric acid, the issue that L-(+)-tartaric acid backbone and (R)-binaphthyl showed strong matched/mismatched character was solved with these tropos ligands. It was found that the enantioselectivity was mainly controlled by the absolute configuration of N-benzyltartarimide backbone, and both enantiomers of the addition products can be obtained by simply changing the configuration of N-benzyltartarimide substituent.